WO2020090597A1 - Procédés de production de fibre de précurseur de fibre de carbone et fibre de carbone - Google Patents

Procédés de production de fibre de précurseur de fibre de carbone et fibre de carbone Download PDF

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Publication number
WO2020090597A1
WO2020090597A1 PCT/JP2019/041603 JP2019041603W WO2020090597A1 WO 2020090597 A1 WO2020090597 A1 WO 2020090597A1 JP 2019041603 W JP2019041603 W JP 2019041603W WO 2020090597 A1 WO2020090597 A1 WO 2020090597A1
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Prior art keywords
bath
coagulation
guide
coagulation bath
solution
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PCT/JP2019/041603
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English (en)
Japanese (ja)
Inventor
堀之内綾信
渡邉史宜
沖嶋勇紀
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東レ株式会社
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Priority to US17/287,510 priority Critical patent/US11932971B2/en
Priority to JP2019558640A priority patent/JP7500972B2/ja
Publication of WO2020090597A1 publication Critical patent/WO2020090597A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/32—Apparatus therefor
    • D01F9/328—Apparatus therefor for manufacturing filaments from polyaddition, polycondensation, or polymerisation products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide

Definitions

  • the present invention relates to carbon fibers suitably used for sports applications such as golf shafts and fishing rods, and other general industrial applications, including aircraft members, automobile members, and ship members.
  • carbon fiber Since carbon fiber has higher specific strength and specific elastic modulus than other fibers, it can be used as a reinforcing fiber for composite materials in addition to conventional sports and aviation / space applications, as well as automobiles, civil engineering / construction, pressure vessels and It is being widely applied to general industrial applications such as wind turbine blades, and there is a strong demand for both higher productivity and higher performance.
  • the most widely used polyacrylonitrile (hereinafter sometimes abbreviated as PAN) -based carbon fiber is a spinning solution mainly composed of a PAN-based polymer as a precursor thereof, and a dry-wet spinning method.
  • PAN polyacrylonitrile
  • the improvement of the productivity of PAN-based carbon fibers is carried out in any of the steps of producing carbon fiber precursor fibers, making them flame resistant, or carbonizing them.
  • the dry-wet spinning method can increase the take-up speed as compared with other spinning methods. Since it is possible to obtain a carbon fiber having high strength, it is widely applied as a technique capable of simultaneously improving performance as well as improving productivity.
  • the spinning solution is first extruded into a gas atmosphere (air gap) through a spinneret and then introduced into a coagulation bath, where the take-up direction is changed by a bath guide installed at the bottom of the coagulation bath, and the take-up spinning is performed.
  • a spinning method for drawing out a coagulated fiber bundle to obtain a carbon fiber precursor fiber from a coagulation bath with a ladle.
  • Increasing the take-up speed of the coagulated fiber bundle increases the flow of the coagulation bath liquid (hereinafter referred to as "incidental flow") that accompanies the traveling of the fiber bundle during coagulation. It causes the bundle to break.
  • the productivity can be improved by increasing the number of spinneret holes in addition to the increase in the take-up speed.
  • the increase in the number of filaments increases the associated flow, and thus the same problem causes a limit. That is, in the dry-wet spinning for obtaining the carbon fiber precursor fiber, there is a limit to improve the productivity due to the above factors.
  • Patent Document 1 proposes a technique of increasing the spinning tension by using a PAN-based polymer having a specific molecular weight distribution so as to prevent breakage of the fiber bundle during solidification.
  • Patent Document 2 proposes a technique of using a flow-down type coagulation bath to improve the take-up speed by reducing the coagulation bath resistance as much as possible.
  • Patent Document 3 discloses a technique in which a plate having pores or the like surrounds all or part of a fiber bundle during solidification spun downward from a spinneret to suppress fluctuations in liquid level and fluctuations of the fiber bundle during solidification. Proposed.
  • Patent Document 1 Although speeding up is possible, it was necessary to use a specific PAN-based polymer.
  • the technique of Patent Document 2 has a problem that the structure of the coagulation bath is complicated and the industrial feasibility is poor, and a technique is required for threading at the start of work, which deteriorates operability.
  • Patent Document 3 since the effect of suppressing the sinking of the liquid surface is small, the spinning solution extruded from the spinneret in the air gap part breaks, and there is a limit to the improvement in productivity. That is, any of the conventionally known methods was insufficient for producing the carbon fiber precursor fiber with high productivity.
  • an object of the present invention is to break the spinning solution extruded from the spinneret in the air gap part or to coagulate the bath solution even when the spinning speed is increased or the number of holes in the spinneret is increased. It is intended to provide a method for producing a carbon fiber precursor fiber that can be spun without breaking the fiber bundle during solidification, and a carbon fiber using the same.
  • a method for producing a carbon fiber precursor fiber is a polyacrylonitrile-based polymer solution is extruded into the air from a spinneret, immersed in a coagulation bath solution stored in a coagulation bath, and a fiber being coagulated. After folding back with a guide in the first bath installed below the spinneret as a bundle and drawing out from the coagulation bath solution into the air to obtain a coagulated fiber bundle, at least a washing step, a stretching step, an oil agent applying step and a drying step are performed.
  • a method for producing a carbon fiber precursor fiber wherein the spinning solution is immersed in a coagulating bath solution and the fiber bundle during coagulation is the distance from the guide to the coagulating bath depth soaking length It is characterized in that it is 3 to 40 cm.
  • the method for producing a carbon fiber precursor fiber according to the first preferred embodiment of the present invention further includes a coagulation bath oblique immersion for the distance from when the fiber bundle during coagulation is folded back by the guide in the first bath to when it is drawn into the air.
  • the coagulation bath immersion length which is the sum of the coagulation bath depth immersion length and the coagulation bath oblique immersion length, is set to 10 to 500 cm.
  • the method for producing a carbon fiber precursor fiber according to the second preferred embodiment of the present invention further comprises folding the fiber bundle during coagulation with the guide in the first bath, and further using at least a guide in the second bath. Folding back, the second bath guide, characterized in that it is installed in the coagulation solution below the line connecting the point where the fiber bundle during coagulation is drawn into the air from the coagulation solution and the first bath guide To do.
  • the method for producing a carbon fiber of the present invention is a method in which the carbon fiber precursor fiber obtained by the above-mentioned method for producing a carbon fiber precursor fiber is subjected to flame resistance treatment in an oxidizing atmosphere at a temperature of 200 to 300 ° C. , A pre-carbonization treatment in an inert atmosphere at a temperature of 500 to 1200 ° C., and then a carbonization treatment in an inert atmosphere at a temperature of 1200 to 3000 ° C.
  • the spinning solution extruded from the spinneret in the air gap portion does not break or the fiber bundle during coagulation in the coagulating bath solution does not break, and the fiber is stably spun. It is possible to produce high-quality carbon fiber precursor fibers and carbon fibers.
  • the inventors of the present invention even under conditions with a large number of spinneret holes and high take-off speed, break the spinning solution extruded from the spinneret in the air gap part or break the fiber bundle during coagulation in the coagulation bath solution.
  • the present invention has been achieved as a result of repeated intensive studies in order to produce a carbon fiber precursor fiber.
  • FIG. 1 is a side sectional view showing an example of an embodiment of a dry-wet spinning device according to a first preferred aspect of the present invention.
  • the first preferred aspect of the present invention may be abbreviated as aspect (1) hereinafter.
  • reference numeral 1 is a spinneret
  • 2a is a spinning solution
  • 2b is a fiber bundle in which the spinning solution is coagulating
  • 2c is a coagulating fiber bundle
  • 3 is First bath guide in coagulation bath liquid
  • 4 is a center point of the first bath guide 3 (hereinafter, 4 may be abbreviated as the first bath guide center)
  • 5 is a take-off guide
  • 6 is a coagulation bath.
  • Liquid Liquid
  • 7 is air gap length
  • 8 is coagulation bath depth immersion length
  • 9 is coagulation bath oblique immersion length
  • 10 is distance from outermost hole in spinneret take-up direction to center of spinneret
  • 11 is spinneret take-up direction
  • 12 is from the center of the spinneret in the first bath
  • Guide 5 is the angle formed between the straight line which connects a straight line wrapping angle (B) (hereinafter, folding angle 12 in aspects (1) (B) may be abbreviated in some as) a.
  • B straight line wrapping angle
  • 2a, 2b, and 2c are continuous, but are in the following ranges, respectively: 2a: from the spinneret to the coagulation bath liquid, 2b: from the coagulation bath liquid to the coagulation bath liquid exit 2c: After leaving the coagulation bath solution.
  • the spinning solution 2a discharged from the spinneret 1 enters the coagulation bath solution, becomes a fiber bundle 2b during coagulation, travels downward in the coagulation bath solution, and travels toward the take-up guide 5 via the in-bath guide 3 To do.
  • the fiber bundle during coagulation is a fiber bundle in which the spinning solution is coagulating, that is, the spinning solution is immersed in the coagulation bath solution and at least the surface is in a coagulated state. It is in the process of coagulation progressing as the spinning solvent is extracted in. Note that, depending on the conditions, even when the coagulation is completed before leaving the coagulation bath solution, in the present invention, it is referred to as a fiber bundle during coagulation in the coagulation bath solution.
  • the coagulation bath immersion length in aspect (1) is the sum of the coagulation bath depth immersion length 8 and the coagulation bath oblique immersion length 9.
  • the coagulation bath depth immersion length 8 is the vertical distance from the surface of the coagulation bath liquid to the guide center 4 in the first bath, and can be determined by measuring with a tape measure or the like.
  • the liquid level of the coagulation bath solution immediately below the spinneret may sink due to the running of the fiber bundle during coagulation.
  • the liquid level before sinking is the liquid level of the coagulation bath solution.
  • the diagonal dipping length 9 of the coagulation bath is the shortest position with respect to the guide center 4 in the first bath on a straight line which is a traveling path of the fiber bundle during coagulation between the guide 3 in the first bath and the take-up guide 5. It represents the distance from the point to the intersection of the straight line and the liquid surface, and can be determined by measuring with a tape measure or the like.
  • the spinning speed is high, the liquid level when the coagulated fiber bundles come out from the coagulation bath solution into the air may rise. In that case, the liquid level before the coagulation bath solution rises is the liquid level of the coagulation bath solution.
  • FIG. 2 is a side sectional view showing an example of an embodiment of a dry-wet spinning device according to a second preferred aspect of the present invention.
  • the 2nd preferable aspect of this invention may be abbreviated as the aspect (2) hereafter.
  • the spinning aspect until the spinning solution 2a discharged from the spinneret 1 reaches the guide 3 in the first bath as the fiber bundle 2b during coagulation is the same as the spinning aspect of the aspect (1).
  • Folding angle (B) (a) in the mode (2) which is an angle formed by a straight line connecting the points and a straight line connecting the turning point of the fiber bundle 2b during solidification in the first bath guide and the second bath guide 14
  • 16 may be abbreviated as the folding angle (B) in the aspect (2)
  • 17 is the depth of the guide in the second bath
  • 18 is the second oblique dipping length of the coagulation bath.
  • the coagulation bath depth immersion length 8 in aspect (2) is the same as in aspect (1).
  • the second in-bath guide 14 in the aspect (2) is installed in the coagulation bath solution below the straight line connecting the point where the fiber bundle during coagulation is drawn out of the coagulation bath solution into the air and the first in-bath guide.
  • the coagulation bath first oblique immersion length 13 in the aspect (2) is a length of a line segment connecting the first bath guide center 4 and the second bath guide center 15, and is determined by measuring with a tape measure or the like. it can.
  • the second coagulation bath second oblique immersion length 18 is the shortest position with the second bath guide center 15 on a straight line which is a traveling path of the fiber bundle during coagulation between the second bath guide 14 and the take-up guide 5. It represents the distance from the point to the intersection of the straight line and the liquid surface, and can be determined by measuring with a tape measure or the like.
  • the second bath guide depth 17 is the vertical distance between the second bath guide center 15 and the surface of the coagulating liquid, and can be measured with a tape measure or the like.
  • the coagulation bath depth immersion length 8 in the aspect (1) is 3 to 40 cm.
  • the coagulation bath depth immersion length 8 is preferably 3 to 30 cm, more preferably 4 to 25 cm, and further preferably 5 to 20 cm.
  • the immersion length of the coagulation bath is preferably 10 to 500 cm, more preferably 15 to 300 cm, even more preferably 20 to 200 cm.
  • the folding angle (B) in the aspect (1) is preferably 70 ° to 89 °, more preferably 75 ° to 89 °, and further preferably 80 ° to 89 °. If the turn-back angle (B) in mode (1) is too small, the distance between the fiber bundle 2b during coagulation running from the first bath guide 3 toward the take-up guide 5 and the liquid level of the coagulation bath liquid becomes short, and the liquid surface Of the coagulation bath and breakage of the fiber bundle during solidification, while too large, the size of the coagulation bath used becomes large.
  • the coagulation bath depth immersion length 8 is 3 to 40 cm. If the coagulation bath depth dipping length is shortened, the accompanying flow in the coagulation bath depth direction is reduced, and the fiber bundles are less likely to break during coagulation. However, if it is too short, it passes through the first bath guide 3 and the second bath bath. The distance between the fiber bundle during coagulation running toward the guide and the liquid surface of the coagulation bath liquid becomes too close, and the liquid surface fluctuation in the vicinity of the spinneret increases, resulting in unevenness in the weight. Therefore, the immersion depth of the coagulation bath is preferably 3 to 30 cm, more preferably 4 to 25 cm, and further preferably 5 to 20 cm.
  • the first diagonal immersion length 13 of the coagulation bath is preferably 10 to 300 cm, more preferably 10 to 250 cm, still more preferably 10 to 150 cm.
  • the second oblique immersion length 18 of the coagulation bath is uniquely determined by the position of the guide 14 in the second bath and the position of the take-up guide 5. The positions of both guides are not particularly limited and may be appropriately determined from the viewpoint of operability. However, in order to obtain the effect according to the aspect (2), the position where the coagulated fiber bundle is drawn out of the coagulation bath liquid into the air is set. It is preferably installed in the coagulation bath liquid below the straight line connecting the guide in the first bath.
  • the folding angle (B) in the aspect (2) is preferably 70 ° to 150 °, more preferably 80 ° to 140 °, and further preferably 90 ° to 130 °. If the folding back angle (B) is too small, the distance between the fiber bundle during coagulation running from the guide in the first bath toward the guide in the second bath and the liquid surface of the coagulating bath liquid becomes close, and the liquid surface fluctuates, resulting in unevenness of the weight. On the other hand, while the fiber bundle is broken during solidification, and if it is too large, the flow in the depth direction immediately below the mouthpiece increases, and as a result, the liquid level fluctuates, causing unevenness in the fabric and breakage of the fiber bundle during solidification. I will end up.
  • the condition where the turn-back angle (B) is smaller than 90 ° can be adopted in the mode (1), but in the mode (1), the coagulation bath size needs to be increased as the turn-back angle (B) approaches 90 °.
  • the aspect (2) is different in that the coagulation bath size does not have to be forcibly changed according to the folding back angle (B).
  • the aspect (2) has a feature that the turning angle (B) in the first in-bath guide can be increased as compared with the aspect (1), and the fiber bundle during coagulation and the liquid surface during traveling in the take-up guide direction Is more advantageous than the embodiment (1), and the spinnability can be further improved. Further, since the frictional resistance in the guide in the first bath can be reduced by increasing the folding back angle (B), there is an advantage in that the yarn quality can be improved. Therefore, the second bath guide may be installed for the purpose of increasing the turnaround angle (B) in the first bath guide, and then the third bath guide and the fourth bath guide are installed. Then, the device for controlling the running of the fiber bundle during solidification may be devised.
  • the polyacrylonitrile polymer constituting the polyacrylonitrile polymer solution used in the present invention is polyacrylonitrile, a copolymer containing polyacrylonitrile as a main component, or a mixture containing them as a main component.
  • polyacrylonitrile may be abbreviated as PAN.
  • the term "main component” as used herein means a component contained in the mixture or copolymer in an amount of 60% by mass or more.
  • the solvent of the PAN-based polymer solution is not particularly limited as long as it can dissolve the PAN-based polymer, and for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, zinc chloride aqueous solution, and sodium thiocyanate aqueous solution may be used. it can.
  • the temperature of the PAN-based polymer solution when discharged from the die is not particularly limited, and may be appropriately determined from the viewpoint of discharge stability.
  • the number of holes of the die used in the present invention is preferably 500 to 24,000. If the number of holes is less than 500, it is necessary to install a large number of spinnerets, and the workability such as threading when trouble occurs is deteriorated. On the other hand, when the number of holes exceeds 24,000, the die may become too large, and there is a concern that unevenness in the weight of the die may occur at the center portion and the outer peripheral portion of the die.
  • the shape of the region in which the mouth hole is arranged may be circular, rectangular, or annular, but the rectangle has long sides and short sides, and it is common to arrange the short side in the yarn bundle take-up direction. Is.
  • the length in the take-up direction of the spinneret is 5 to 20 cm.
  • the length in the take-up direction of the spinneret is the outermost hole and the front side on the rear side with respect to the direction in which the spinning solution is introduced into the coagulation bath solution and folded back as a fiber bundle during coagulation in the bath guide and then toward the take-up guide.
  • the length between the outermost hole on the side and the outermost hole is shown and can be measured with a tape measure or the like.
  • the coagulation bath liquid in the present invention preferably has a viscosity of 2 to 100 mPa ⁇ s. If the viscosity of the coagulation bath liquid is too low, the denseness of the coagulated fiber is lowered and the physical properties of the final carbon fiber are lowered.
  • the coagulation bath solution may be conventionally referred to as a coagulation bath.
  • the temperature of the coagulation bath solution in the present invention is preferably ⁇ 40 to 80 ° C.
  • the lower the temperature of the coagulation bath solution the more dense the coagulated fibers will be and the final physical properties of the carbon fibers will be improved.
  • the temperature of the coagulation bath solution is low, the viscosity of the coagulation bath solution may increase too much. Since the flow is increased too much, the spinning solution may be broken at the air gap portion or the fiber bundle may be broken during solidification. Therefore, the temperature of the coagulation bath solution is more preferably ⁇ 20 to 50 ° C., further preferably ⁇ 5 to 15 ° C.
  • the coagulation bath solution in the present invention includes a solvent for the PAN-based polymer such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, an aqueous solution of zinc chloride, and an aqueous solution of sodium thiocyanate used as a solvent in the PAN-based polymer solution, and so-called coagulation acceleration.
  • a solvent for the PAN-based polymer such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, an aqueous solution of zinc chloride, and an aqueous solution of sodium thiocyanate used as a solvent in the PAN-based polymer solution, and so-called coagulation acceleration.
  • a mixture of the ingredients is used.
  • the coagulation promoting component those which do not dissolve the above-mentioned PAN-based polymer and are compatible with the solvent used for the PAN-based polymer solution are preferable.
  • the coagulation accelerating component examples include water, methanol, ethanol, ethylene glycol, propylene glycol, glycerin and the like, but it is most preferable to use water from the viewpoint of safety.
  • the solvent concentration of the coagulation bath solution may be appropriately determined from the viewpoint of the compactness and roundness of the coagulated fiber, but when the coagulation promoting component is water and the solvent is dimethyl sulfoxide, dimethylformamide, or dimethylacetamide, the solvent is The concentration is preferably 25 to 85% by mass, more preferably 70 to 85% by mass.
  • the salt concentration is preferably 5 to 60% by mass.
  • the coagulation bath solution is an aqueous solution of zinc chloride or an aqueous solution of sodium thiocyanate, the effect of the present invention becomes particularly remarkable in a salt concentration range of 5 to 60% by mass, which is preferable.
  • the material, shape, and size of the in-bath guide are not particularly limited as long as they are those commonly used in conventional dry-wet spinning, but the coagulation in the guide is the one with the least friction with the fiber bundle during coagulation. It is preferable because breakage of the medium fiber bundle can be suppressed.
  • a roller-type guide may be used to reduce the guide resistance.
  • the angle (A) formed by the straight line connecting the outermost hole in the take-up direction of the spinneret and the turning point of the fiber bundle during solidification in the first bath guide and the line perpendicular to the spinneret surface Is preferably set to 6.5 to 45 °.
  • the angle formed by the straight line connecting the outermost hole in the take-out direction of the spinneret and the turning point of the fiber bundle during solidification in the first bath guide and the line perpendicular to the spinneret surface (A ) May be simply abbreviated as an angle (A).
  • the angle (A) is an angle represented by reference numeral 11 in FIGS. 1 and 2.
  • the air gap length is a distance indicated by reference numeral 7 in FIGS. 1 and 2, and the liquid level of the coagulation bath liquid is caused by an accompanying flow generated as the spinning solution travels in the depth direction of the coagulation bath. It represents the distance between the surface of the coagulation bath solution before sinking and the spinneret. Further, the distance from the outermost hole in the take-up direction of the spinneret to the center of the spinneret, the immersion depth in the coagulation bath and the air gap length can be measured with a tape measure or the like. If the angle (A) is too small, the running spinning solution spreads and the accompanying flow increases, which induces breakage of the fiber bundle during coagulation.
  • the angle (A) is too large, the ejection angle of the spinning solution becomes too large and spinning occurs in the air gap.
  • the spinning solution 2a extruded from the spinneret breaks. Therefore, it is preferably 8 to 40 °, more preferably 10 to 35 °. If the air gap length is too large, it causes breakage of the spinning solution 2a extruded from the spinneret at the air gap portion, so it is preferably 1 to 50 mm.
  • the take-up speed of the spinning solution (normally equal to the take-up speed of the fiber bundle during coagulation) when introducing the PAN-based polymer solution into the coagulation bath liquid to form the fiber bundle during coagulation is 10 m / min or more.
  • the take-up speed of the spinning solution is the surface speed of a roller with a driving source at which the spinning solution leaves the spinneret and the flocculating fiber bundle or the flocculating fiber bundle first contacts.
  • Cheap The spinning draft rate is not particularly limited and may be appropriately determined according to the fineness of the carbon fiber precursor fiber to be produced. The spinning draft rate can be calculated as follows.
  • Spinning draft rate (spinning solution take-up speed) / (discharge linear velocity)
  • the discharge linear velocity is a value obtained by dividing the volume of the spinning solution discharged from the spinneret per unit time by the area of the spinneret hole.
  • a dry heat drawing step or a steam drawing step may be added. Stretching in the bath can usually be performed in a single stretching bath or a plurality of stretching baths whose temperature is controlled at 30 to 98 ° C. At that time, the draw ratio in the bath is preferably 2 to 6 times.
  • an oil agent made of silicone or the like it is preferable to apply one containing a modified silicone such as an amino-modified silicone having high heat resistance.
  • a known method can be used for the subsequent drying step.
  • the heating heat medium for example, pressurized steam or superheated steam is preferably used in terms of operation stability and cost.
  • the carbon fiber precursor fiber produced by the above-mentioned method is preferably subjected to flameproofing treatment in an oxidizing atmosphere at a temperature of 200 to 300 ° C., and then preferably in an inert atmosphere at a temperature of 500 to 1200 ° C.
  • the carbon fiber can be produced by pre-carbonization and then carbonization in an inert atmosphere at a maximum temperature of preferably 1200 to 3000 ° C.
  • Air is preferably adopted as the oxidizing atmosphere in the flameproofing treatment.
  • the preliminary carbonization treatment and the carbonization treatment are performed in an inert atmosphere.
  • the gas used in the inert atmosphere include nitrogen, argon and xenon, and nitrogen is preferably used from the economical viewpoint.
  • graphitization may be performed following the carbonization step. The graphitization step is preferably carried out at a temperature of 2000 to 3000 ° C.
  • the obtained carbon fiber can be subjected to electrolytic treatment for surface modification. This is because the electrolytic treatment can optimize the adhesiveness with the carbon fiber matrix in the obtained fiber-reinforced composite material.
  • a sizing treatment may be performed in order to provide the carbon fibers with a focusing property.
  • a sizing agent having a good compatibility with the matrix resin can be appropriately selected according to the type of resin used.
  • Example 1 ⁇ Spinning solution> Acrylonitrile and itaconic acid were copolymerized by a solution polymerization method using dimethylsulfoxide as a solvent and a polymerization initiator to prepare a polyacrylonitrile-based copolymer, which was used as a spinning solution having a polymer concentration of 21% by mass.
  • the spinneret with the short side of the area where the spinneret holes are placed is 6 cm, and the spinneret with 1000 holes is placed with the short side facing in the take-up direction. It was arranged so that the length was 5 mm.
  • the spinning solution prepared as described above was discharged into the air from the spinneret and immersed in a coagulation bath solution whose temperature was controlled at 5 ° C. to take out the coagulated fiber bundle in the spinning mode of aspect (1).
  • the coagulation bath depth immersion length was 10 cm
  • the coagulation bath immersion length was 160 cm.
  • the viscosity of the coagulation bath liquid was 7 mPa ⁇ s
  • the angle (A) formed by the fiber bundle and the guide during coagulation was 15.9 °
  • the folding angle (B) was 86 °.
  • the limit take-up speed which is the take-up speed at that time, was 46 m / min.
  • Example 2 Same as Example 1 except that the depth of immersion in the coagulation bath was 20 cm.
  • Example 3 The same procedure as in Example 1 was performed except that a spinneret having a short side of 9 cm and a hole number of 5,000 was used, and the coagulation bath depth immersion length was 5 cm.
  • Example 4 The procedure of Example 3 was repeated, except that the immersion depth of the coagulation bath was 15 cm.
  • Example 5 The procedure of Example 3 was repeated, except that the depth of immersion in the coagulation bath was 35 cm.
  • Example 6 The depth of immersion in the coagulation bath was 5 cm, and the immersion length in the coagulation bath was 15 cm.
  • Example 7 The same procedure as in Example 1 was performed except that a spinneret having a short side of 15 cm and a hole number of 10,000 was used and the coagulation bath depth immersion length was 10 cm.
  • Example 1 was the same as Example 1 except that the spinneret having a short side of 18 cm and the number of holes of 16000 was used and the depth of immersion in the coagulation bath was 15 cm.
  • Example 9 The same procedure as in Example 1 was carried out except that the coagulation bath liquid used was a mixture of dimethyl sulfoxide 70% by mass and water 30% by mass.
  • the viscosity of the coagulation bath liquid was 12 mPa ⁇ s. Since the concentration of the organic solvent in the coagulation bath liquid is high, the limit take-up speed does not reach when the concentration of the organic solvent is low, but the limit take-up speed is increased by 13 m / min as compared with Comparative Example 5 described later, and the increase range is large. ..
  • Example 10 The same procedure as in Example 1 was carried out except that the coagulation bath liquid used was a mixture of dimethyl sulfoxide 80% by mass and water 20% by mass. The viscosity of the coagulation bath liquid was 11 mPa ⁇ s. The limit take-up speed is increased by 15 m / min as compared with Comparative Example 6 described later, and the increase range is large.
  • Example 11 The same procedure as in Example 1 was carried out except that the coagulation bath liquid used was a mixture of dimethyl sulfoxide (85% by mass) and water (15% by mass). The viscosity of the coagulation bath liquid was 11 mPa ⁇ s. The limit take-up speed is increased by 16 m / min as compared with Comparative Example 7 which will be described later, and the increase range is large.
  • Example 12 As the coagulation bath liquid, the same procedure as in Example 1 was carried out except that 55% by mass of dimethyl sulfoxide, 20% by mass of water and 25% by mass of glycerin (Gly) were mixed and the temperature was controlled at -5 ° C. The viscosity of the coagulation bath liquid was 42 mPa ⁇ s. The limit take-up speed is increased by 17 m / min as compared with Comparative Example 8 which will be described later, and the increase range is large.
  • Example 13 Same as Example 1 except that the solvent of the polyacrylonitrile-based copolymer solution was dimethylformamide, and the coagulation bath liquid was mixed at a ratio of 80% by mass of dimethylformamide and 20% by mass of water, and the temperature was controlled at -5 ° C. did.
  • the viscosity of the coagulation bath liquid was 10 mPa ⁇ s.
  • the limit take-up speed is increased by 17 m / min as compared with Comparative Example 9 which will be described later, and the increase range is large.
  • Example 14 Dimethylacetamide was used as the solvent of the polyacrylonitrile-based copolymer solution, and the coagulation bath liquid was mixed at a ratio of 80% by mass of dimethylacetamide and 20% by mass of water, and the temperature was controlled to 5 ° C, and the same as in Example 1. ..
  • the viscosity of the coagulation bath liquid was 12 mPa ⁇ s.
  • the limit take-up speed is increased by 16 m / min as compared with Comparative Example 10 described later, and the increase range is large.
  • Example 15 The same procedure as in Example 1 was carried out except that 5% by mass of dimethyl sulfoxide and 95% by mass of water were mixed as a coagulation bath solution and the temperature was controlled at 25 ° C. The viscosity of the coagulation bath liquid was 2 mPa ⁇ s.
  • Example 5 was the same as Example 5, except that the spinning depth of the coagulation bath was 35 cm, the first diagonal immersion length of the coagulation bath was 100 cm, and the guide depth in the second bath was 15 cm.
  • the folding angle (B) was 78 °, which was 4 ° larger than that in Example 5.
  • Example 17 Same as Example 16 except that the guide depth in the second bath was 35 cm.
  • the folding back angle (B) was 90 °.
  • Example 16 was the same as Example 16 except that the first oblique immersion length of the coagulation bath was 40 cm and the guide depth in the second bath was 50 cm.
  • the folding back angle (B) was 112 °.
  • Example 19 Same as Example 18 except that the guide depth in the second bath was 60 cm.
  • the folding back angle (B) was 129 °.
  • Example 20 Same as Example 18 except that the guide depth in the second bath was 68 cm.
  • the folding angle (B) was 146 °.
  • Example 16 was the same as Example 16 except that the depth of immersion in the coagulation bath was 15 cm.
  • the folding back angle (B) was 90 °.
  • Example 22 Same as Example 21 except that the guide depth in the second bath was 60 cm.
  • the folding back angle (B) was 117 °.
  • Example 23 Same as Example 16 except that the depth of immersion in the coagulation bath was 5 cm.
  • the folding back angle (B) was 90 °.
  • Example 24 Same as Example 23 except that the guide depth in the second bath was 60 cm.
  • the folding back angle (B) was 123 °.
  • Example 10 was carried out in the same manner as in Example 10 except that the immersion length in the coagulation bath depth was 10 cm, the first oblique immersion length in the coagulation bath was 100 cm, and the guide depth in the second bath was 10 cm in the spinning mode of aspect (2).
  • the folding back angle (B) was 90 °.
  • Example 26 Same as Example 25 except that the first oblique immersion length of the coagulation bath was 40 cm and the guide depth in the second bath was 25 cm.
  • the folding back angle (B) was 112 °.
  • Example 27 Same as Example 25 except that the coagulation bath liquid was mixed at a ratio of 70% by mass of dimethyl sulfoxide and 30% by mass of water.
  • the folding back angle (B) was 90 °.
  • Example 28 The same procedure as in Example 21 was carried out except that the coagulation bath liquid was mixed at a ratio of 80% by mass of dimethyl sulfoxide and 20% by mass of water.
  • the folding back angle (B) was 90 °.
  • Example 1 (Comparative Example 1) The procedure of Example 1 was repeated, except that the depth of immersion in the coagulation bath was 60 cm. The limit take-off speed was reduced by 11 m / min as compared with Example 1 in which the immersion depth was set to 10 cm.
  • Example 2 The procedure of Example 3 was repeated, except that the depth of immersion in the coagulation bath was 60 cm.
  • Comparative example 3 The procedure of Comparative Example 2 was repeated except that a spinneret having a short side of 25 cm and a hole number of 18,000 was used.
  • Comparative example 4 The procedure of Comparative Example 3 was repeated, except that a spinneret having a short side of 25 cm and a hole number of 21,000 was used.
  • Example 5 The procedure of Example 9 was repeated, except that the depth of immersion in the coagulation bath was 60 cm. The limit take-off speed was reduced by 13 m / min as compared with Example 9 in which the immersion depth was set to 10 cm.
  • Example 6 The procedure of Example 10 was repeated except that the depth of immersion in the coagulation bath was 60 cm. The limit take-off speed was reduced by 15 m / min as compared with Example 10 in which the immersion depth was set to 10 cm.
  • Example 7 The procedure of Example 11 was repeated except that the depth of immersion in the coagulation bath was 60 cm. The limit take-off speed was reduced by 16 m / min as compared with Example 11 in which the immersion depth was set to 10 cm.
  • Example 8 The procedure of Example 12 was repeated, except that the depth of immersion in the coagulation bath was 60 cm. The limit take-off speed was reduced by 17 m / min as compared with Example 12 in which the immersion depth was set to 10 cm.
  • Example 9 The procedure of Example 13 was repeated except that the immersion depth of the coagulation bath was 60 cm. The limit take-off speed was reduced by 17 m / min as compared with Example 13 in which the immersion depth was set to 10 cm.
  • Example 10 (Comparative Example 10) The procedure of Example 14 was repeated, except that the depth of immersion in the coagulation bath was 60 cm. The limit take-off speed was reduced by 16 m / min as compared with Example 14 in which the immersion depth was set to 10 cm.
  • Comparative Example 11 The procedure of Comparative Example 2 was repeated, except that the coagulation bath liquid was mixed at a ratio of 80% by mass of dimethyl sulfoxide and 20% by mass of water.
  • Example 13 The procedure of Example 17 was repeated, except that the immersion depth in the coagulation bath was 60 cm, and the guide depth in the second bath was 60 cm.
  • dimethylsulfoxide is abbreviated as DMSO, glycerin as Gly, dimethylformamide as DMF, and dimethylacetamide as DMAC.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Inorganic Fibers (AREA)

Abstract

La présente invention concerne un procédé de production de fibres de précurseur de fibre de carbone qui est capable de filer sans rupture de la solution de filage extrudée par une filière dans une section d'espace d'air, ni rupture du faisceau de fibres en solidification dans une solution de bain de coagulation même lorsque la vitesse de filage est augmentée et/ou que le nombre de trous de filière est augmenté ; et des fibres de carbone l'utilisant. L'invention concerne un procédé de production de fibres de précurseur de fibre de carbone dans lequel une solution de polymère de polyacrylonitrile est extrudée dans l'air par une filière 1, est immergée dans une solution de bain de coagulation dans laquelle une solution de filage est stockée, est repliée sous forme de faisceaux de fibres en solidification par un premier guide dans le bain qui est disposé au-dessous de la filière, et est étirée depuis la solution de bain de coagulation dans l'air pour obtenir des faisceaux de fibres coagulées, puis au moins une étape de rinçage à l'eau, une étape d'étirage, une étape d'application d'huile et une étape de séchage sont appliquées, la longueur d'immersion de profondeur de bain de coagulation, qui est la distance après que la solution de filage ait été immergée dans la solution de bain de coagulation jusqu'à ce qu'elle soit repliée par le premier guide dans le bain 3, étant de 3 à 40 cm.
PCT/JP2019/041603 2018-10-29 2019-10-24 Procédés de production de fibre de précurseur de fibre de carbone et fibre de carbone WO2020090597A1 (fr)

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